Quaternary ammonia salts of polyhalogenated aromatic compounds

ABSTRACT

in the presence of an inert solvent with an alkylation reagent R3X in which the designations Ar, R, R1, R2, R3 have the same meaning as indicated hereinabove. The quaternary ammonium salts of this invention are useful as phytosanitary or plant sanitizing agents. The products are particularly useful as bactericides and fungicides on plants.   in which Ar represents a polyhalogenated aromatic radical such as pentachlorophenyl, octachlorobiphenylene, octabromobiphenylene, hexachlorodibromobiphenylene, dodecachloroterphenylene, etc. R, R1, R2, R3 represent a hydrocarbon aliphatic, cycloaliphatic or arylaliphatic radical or substituted aliphatic, cycloaliphatic or arylaliphatic radical in which substituted groups are selected from heteroatoms such as O or S, or methyl, ethyl, isopropyl, Beta chloroethyl, allyl, methallyl, benzyl, chlorobenzyl, morpholyl, methylthioethyl, groups and so forth, X is a halogenide, an alkylsulfate containing from 1 to 20 carbon atoms or an arylsulfonate anion, and n is an integer from 1 to 3, and a process for manufacturing the above compounds by reacting a tertiary amine of the formula:   New quaternary ammonium salts corresponding to the general formula

United States Patent 1 Isard et al.

[ 51 Dec. 30, 1975 [75] Inventors: Arsene Isard, Grenoble; Ludovic Parvi, Pont-de-Claix, both of France [73] Assignee: Products Chimiques Ugine Kuhlmann, Paris, France [22] Filed: Mar. 15, 1973 [21] Appl. No.: 341,374

Related U.S. Application Data [63] Continuation of Ser. No. 17,935, March 9, 1970,

abandoned.

[30] Foreign Application Priority Data Mar. 18, 1969 France 69.07630 [52] U.S. CI ..260/567.6 R, 567.6 M, 260/5676 P [51] Int. CI. C07C 93/08 [58] Field of Search 260/567.6 R, 567.6 M, 567.6 P

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 2,038,503 l/l97l France 493,865 10/1938 United Kingdom 260/5676 M 672,708 5/l952 United Kingdom 260/5676 M 1,020,031 5/1958 Germany OTHER PUBLICATIONS Ponci et al., Chem. Abstracts, Vol. 61, 8217-8219 (1964).

Primary ExaminerJames 0. Thomas, Jr. Assistant Examiner.lames H. Reamer Attorney, Agent, or Firm-Pennie & Edmonds [57] ABSTRACT New quaternary ammonium salts corresponding to the general formula in which Ar represents a polyhalogenated aromatic radical such as pentachlorophenyl, octachlorobiphenylene, octabromobiphenylene, hexachlorodibromobiphenylene, dodecachloroterphenylene, etc. R, R R R represent a hydrocarbon aliphatic, cycloaliphatic or arylaliphatic radical or substituted aliphatic, cycloaliphatic or arylaliphatic radical in which substituted groups are selected from heteroatoms such as O or S, or methyl, ethyl, isopropyl, Bchloroethyl, allyl, methallyl, benzyl, chlorobenzyl, morpholyl, methylthioethyl; groups and so forth, X is a halogenide, an alkylsulfate containing from 1 to 20 carbon atoms or an arylsulfonate anion, .and n is an integer from I to 3, and a process for manufacturing the above compounds by reacting a tertiary amine of the formula:

in the presence of an inert solvent with an alkylation reagent R X in which the designations Ar, R, R R R have the same meaning as indicated hereinabove.

The quaternary ammonium salts of this invention are useful as phytosanitary or plant sanitizing agents. The products are particularly useful. as bactericides and fungicides on plants.

6 Claims, No. Drawings QUATERNARY AMMONIA SALTS OF POLYHALOGENATED AROMATIC COMPOUNDS This is a continuation, of application Ser. No. 17,935,

filed Mar. 9, 1970, now abandoned.

SUMMARY OF THE INVENTION The present invention relates to new quaternary ammonium salts corresponding to the general formula in which Ar represents a polyhalogenated aromatic radical such as pentachlorophenyl, octachlorobiphenylene, octabromobiphenylene, hexachlorodibromobiphenylene, dodecachloroterphenylene, etc. ,R, R R R represent a hydrocarbon aliphatic, cycloaliphatic or arylaliphatic radical or substitutedaliphatic, cycloaliphatic or arylaliphatic radical in which substituted groups are selected from heteroatoms such as O or S, or methyl, ethyl, isopropyl, Bchloroethyl, allyl, methallyl, benzyl, chlorobenzyl, morpholyl, methylthi oethyl, groups and so forth, X is a halide, an alkylsulfate containing from 1 to 20 carbon atornsor an arylsulfonate anion, and n is an=integer from 1 to 3.

The invention also includes a process for manufacturing the above compounds by reacting a tertiary amine of the formula in the presence of an inert solvent with analkylation reagent R X in which the designations Ar, R, R R R and n have the same meaning as indicated above and in which X is a halogen such as chlorine, bromine, iodine or fluorine, an alkyl sulfate radical containing 1 to 20 carbon atoms or an aryl sulfonate radical.

DETAILED DESCRIPTION OF THE INVENTION The amines of formula (II) from which the novel products of this invention are obtained can be prepared in known manners by those skilled in the art. One manner by which these amines can be easily produced is disclosed in copending United States application Ser. No. 820,310, filed Apr. 29, i969. The abovev U.S. application is assigned to the same assignee as the present application and the contents thereof are incorporated herein by reference.

The reaction to produce the quaternary ammonium products of this invention can be carried out in the presence of inert solvents such as benzene, monochlorobenzene, dioxane, carbon tetrachloride, etc. In place of the inert solvent an excess of the alkylation reactant R X can also be advantageously employed.

The reaction conditions (time, temperature, pressure, etc.) which can be employed to form the new quaternary ammonium salts of this invention can be varied quite widely and will depend mainly upon the particular alkylation reactant R X being used to react with the amines of formula (II). For example, the reaction is quite rapid when allyl chloride is used as the 2 alkylating agent and fairly slow and sometimes incomplete when the alkylating reagent used is dichlorethane. The temperature of the reaction between the amine of formula (II) and the alkylating agent is generally determined by the boiling point of the solvent when the reaction is being carried out under atmospheric conditions but the reaction temperature can of course be higher if the reaction is carried outunder pressure. It is generally advantageous to carry out the reaction at a temperature ranging between about 50 and 250C.

The new quaternary ammonium salts of this invention are useful as phytosanitary or plant sanitizing agents. The products are particularly useful as bactericides and fungicides on plants. The new quaternary ammonium salts of this invention can be used in the original form but it is preferable to utilize the products in the form of solutions, emulsions, powders, pastes,

granules, and so forth and can be readily produced in these forms for application by manners well known to those skilled in the art.

The following examples further illustrate the quaternary ammonium salts and methodsof preparation according to the invention.

EXAMPLE I gms. of decachlorobiphenyl, 44.5 gms. of N,N- dimethyl ethanolamine, 28 gms. of NaOH, in flakes, and 310 cm of dioxane were placed in a reactor. These compounds were kept at the boiling point for 3 /2 hours, then filtered and, the reaction mixture neutralized with C0 The resulting precipitate was then washed several times by decantation in distilled water, and then dissolved in methylene chloride. The solution was evaporated, and 147 gms. of the eondensati'onproduct recovered which titrated 48.6 percent chlorine and 4.1 nitrogen.

EXAMPLE II lonizable chlorine Nitrogen Total chlorine 0.22 eq/lOO gms. 3.2 percent 47.] percent and was mainly a quaternary ammonium salt of the following 9 tI uctuIe.

EXAMPLE III A mixture of 57 gms. of the amine compound, as produced in Example I, and 150 gms. of diehloro-LZ ethane were kept'boiling at reflux for a period of l0 hours in a suitable reaction vessel. After cooling, the reaction mixture was treated with ether in order to 4 eliminate the dichloroethane and the amine which did I o h amines coming i hi h scope bffo l 1 not react. The paste-like solid which was left was can be prepared in the same manner as set forth for washed in ether and then dried 30 gms. ofa solid were preparing the amines in Examples l and IV as will be thus obtained Consisting essentially of the quaternary apparent to those skilled in the art. ammonium salt of the following structure: t 5 We Claimi H C1 H s a V s 6 c1 cii -cn -nicn -cu CH -CH \CH -CH C1 2c1 ca; cu

containing:

'Qnlzable chlmine 0-221 eq/mo 1. Quaternary ammonium salts corresponding to the Nitrogen 3.59 percent l f l Total chlorine 50.3 percent genera Ormu 1 t g 1 Q: Rqi-n-o O-R-N R x R g v I 2 EXAMPLE IV in which the biphenyl radical is polyhalogenated; R is a lower alkylene group; R R and R each represents an unsubstituted alkyl or cycloalkyl radical, or a halogen dlmethyl'ethanolamme! 28 of NaOH m flakes substituted alkyl or cycloalkyl radical, or a lower alkyl and 500 of dloxane were Placed in a reaction substituted cycloalkyl radical; and X is a halide, an

The mixture was k p P p alkylsulfate containing from 1 to 20 carbon atoms or an for 3% hours the reaction mixture then further treated l 'lf t anion.

in'the same manner as set forth in Example I. The final P f wa dlmethylamlno'zethoxy'pema 30 2. Quaternary ammonium salts according to claim 1 chlorobcnzene' in which the biphenyl radical is perhalogenated.

' l42 gms. of hexachlorobenzene, 44.5 gms. of N-N- EXAMPLE V A mixtur eiof gms. of the amine obtained in Example lVan'd 120 gms of allyl chloride were heated under reflux for 10 hours in a suitable reaction vessel. After 3. Quaternary ammonium compound of claim 2 wherein R is a monosubstituted chloroallyl radical.

cooling the reaction i t 72 gms, f a white solid 4. Quaternary ammoniumsalts according to claim 2 wasse aratdb Flt't' mula p e y l ra corresponding the for in which R,, R and R each represent a unsubstituted c1 c" 40 or halo substituted lower alkyl radical of from 1 to 3 i 9/ 43 Y 6 carbon atoms, X is a halide. @J CH -CH u-ca cu cs c1 y x 5. A quaternary ammonium salt of the formula:

H, 0/ Cl 9 3 e CH =CH- CH -N-C -CH -0 -O- CH -CI-l -I:ICI-l -CH=CH 2C1 CH CH containing: 6. The quaternary ammonium compound having the formula CH 1 /CH 6/ 6 9 C1 CH -CH -N-CH CH CH -CH -N-CH -CH C1,2C1

CH 3 I I CH 3 llGrnizahle chlorine 013 eqlloo gms.

iirogen 3. a Total chlorine SO iI SLi'ZZhI Ethylenic groups 0.27 eq/IOO gms.

UNITED STATESPATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,929,886

DATED I December 30, 1975 V 1 ARSENE ISARD ET AL.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 1 a 1 First page amend the "Assignee" toread' Produits Chimiques Ugine Kuhlmann, Paris, France Column 1, line 27, delete "X'" and substitute therefor Column 2, line 34, delete "147" and substitute therefor Columnv 4, line 26, delete "X""' and substitute therefor Column 4, claim 5, line 2, amend the right-hand moiety to read as follows: I I I 101-1 I Signcdjnd Scaled this Twentj fourth Day of August 1976 '[SEAL] r RUTH C; MASON a c. MARSHALL DANN Arresting Officer Cumrrzissinner uj'Patems and Trademarks 

1. QUARTERNARY AMMONIUM SATS CORRESPONDING TO THE GENERAL FORMULA:
 2. Quaternary ammonium salts according to claim 1 in which the biphenyl radical is perhalogenated.
 3. Quaternary ammonium compound of claim 2 wherein R3 is a monosubstituted chloroallyl radical.
 4. Quaternary ammonium salts according to claim 2 in which R1, R2 and R3 each represent a unsubstituted or halo substituted lower alkyl radical of from 1 to 3 carbon atoms, X is a halide.
 5. A quaternary ammonium salt of the formula:
 6. The quaternary ammonium compound having the formula 